TECHNICAL FIELD
[0001] The present disclosure relates to a divalent phosphazenium salt and a method for
producing the same. It also relates to a polyalkylene oxide composition containing
the divalent phosphazenium salt, and a method for producing the same, as well as a
polyurethane-forming composition containing the polyalkylene oxide composition.
BACKGROUND ART
[0002] Monovalent phosphazenium salts are known as useful organic bases.
[0003] For example, Patent Document 1 discloses a method for producing a polyoxyalkylene
oxide by conducting a polymerization reaction of an alkylene oxide using a monovalent
phosphazenium salt having a specific structure represented by the formula (I).

[0004] Further, Patent Document 2 discloses a method for producing a polyoxyalkylene polyol,
characterized by addition-polymerizing an epoxide compound to an active hydrogen compound
using a compound having a P=N bond as a catalyst, to produce a crude polyoxyalkylene
polyol, and then contacting the crude polyoxyalkylene polyol and a predetermined solid
acid, to control the residual amount of the catalyst in the polyoxyalkylene polyol
to be at most 150 ppm. Patent Document 2 discloses a monovalent phosphazenium salt
as the compound having a P=N bond.
[0005] Furthermore, a polyalkylene oxide composition containing a phosphazenium salt and
a polyalkylene oxide is known.
[0006] Patent Document 1 discloses a method for producing a polyalkylene oxide by using
a monovalent phosphazenium salt having a specific structure as a catalyst to produce
a polyalkylene oxide, and then removing the phosphazenium salt by means of an adsorbent.
The polyalkylene oxide according to Patent Document 1 is a polyalkylene oxide having
a pH within a predetermined range and being excellent in urethanization reactivity.
[0007] Patent Document 2 discloses a method for producing a polyoxyalkylene polyol, characterized
by addition-polymerizing an epoxide compound to an active hydrogen compound using
a compound having a P=N bond as a catalyst, to produce a crude polyoxyalkylene polyol,
and then contacting the crude polyoxyalkylene polyol and a predetermined solid acid,
to control the residual amount of the catalyst in the polyoxyalkylene polyol to be
at most 150 ppm, and the polyoxyalkylene polyol obtainable by the production method.
PRIOR ART DOCUMENTS
PATENT DOCUMENTS
[0008]
Patent Document 1: Japanese Patent No. 5716382
Patent Document 2: Japanese Patent No. 4201233
DISCLOSURE OF INVENTION
TECHNICAL PROBLEM
[0009] However, the monovalent phosphazenium salts according to Patent Documents 1 and 2
have been removed from the produced polyalkylene oxides because the monovalent phosphazenium
salts exhibit strong basicity. Therefore, there is a need for a neutral phosphazenium
salt which is not required to be removed.
[0010] By the way, a polyalkylene oxide is useful as a raw material for a resin such as
polyurethane or polyester, and its applications include products to be used indoors
and in vehicles. The polyalkylene oxide or a resin using the same is strongly required
to reduce aldehydes to be generated in living spaces such as indoors and in vehicles.
[0011] Further, since the resin may be exposed to a high temperature in a process for producing
a product in which such a resin is to be used, it is desired to be excellent in thermal
stability.
[0012] Therefore, one aspect of the present invention is directed to providing a divalent
phosphazenium salt which is neutral and is excellent in thermal stability and aldehyde
scavenging ability, and a method for producing the same.
[0013] Further, as a result of further studies by the present inventors regarding the polyalkylene
oxide according to Patent Document 1 or 2, it has been found that the polyalkylene
oxide has room for further improvement in reducing the amount of volatile aldehydes.
There is a strong demand for reducing aldehydes to be generated in living spaces such
as indoors and in vehicles.
[0014] Further, a polyalkylene oxide is useful as a raw material for urethane or the like,
and its applications include products to be used indoors and in vehicles, and therefore,
suppression of generation of odor and turbidity is desired.
[0015] Therefore, one aspect of the present invention is directed to providing a polyalkylene
oxide composition in which the amount of volatile aldehydes is reduced, the generation
of odor and turbidity is suppressed, and the urethane-forming reactivity is excellent.
Another aspect of the invention is directed to providing a method of producing such
a polyalkylene oxide composition. Yet another aspect of the present invention is directed
to providing a polyurethane-forming composition that contributes to formation of a
polyurethane having odor and turbidity reduced.
SOLUTION TO PROBLEM
[0016] The divalent phosphazenium salt according to one embodiment of the present invention
is:
- [1] a divalent phosphazenium salt represented by the formula (1):

in formula (1),
R1 and R2 represent each independently a hydrogen atom, a C1-20 hydrocarbon group, a ring structure in which R1 and R2 are bonded to each other, or a ring structure in which a plurality of R1 or R2 are bonded to each other;
An- represents a deprotonated form of an organic sulfonic acid or organic disulfonic
acid;
either one of n and m is 1, and the other is 2; and
a is 2 when Y is a carbon atom and 3 when Y is a phosphorus atom.
- [2] A divalent phosphazenium salt represented by the formula (2):

in the formula (2),
R1 and R2 represent each independently a hydrogen atom, a C1-20 hydrocarbon group, a ring structure in which R1 and R2 are bonded to each other, or a ring structure in which a plurality of R1 or R2 are bonded to each other; and
A- represents a deprotonated form of an organic sulfonic acid.
- [3] A divalent phosphazenium salt represented by the formula (3):

in the formula (3),
R1 and R2 represent each independently a hydrogen atom, a C1-20 hydrocarbon group, a ring structure in which R1 and R2 are bonded to each other;
An- represents a deprotonated form of an organic sulfonic acid or organic disulfonic
acid; and
either one of n and m is 1 and the other is 2.
- [4] The divalent phosphazenium salt according to any one of [1] to [3], characterized
in that
R1 and R2 are methyl groups, and
An- or A- is a deprotonated form of a dodecylbenzenesulfonic acid, a linear alkylbenzenesulfonic
acid (soft type), or a branched chain alkylbenzenesulfonic acid (hard type).
- [5] The divalent phosphazenium salt according to any one of [1] to [4], characterized
in that the pH of a 0.01 mol/L aqueous solution of the divalent phosphazenium salt
is at least 5 and at most 8.
- [6] An aldehyde scavenger containing the divalent phosphazenium salt as defined in
any one of [1] to [5].
- [7] A method for producing the divalent phosphazenium salt as defined in any one of
[1] to [5], characterized by reacting at least 2 mol of an organic sulfonic acid to
1 mol of the phosphazenium salt represented by the formula (4):

in the formula (4),
R1 and R2 represent each independently a hydrogen atom, a C1-20 hydrocarbon group, a ring structure in which R1 and R2 are bonded to each other, or a ring structure in which a plurality of R1 or R2 are bonded to each other;
X- represents a hydroxy anion, a C1-4 alkoxy anion, a carboxy anion, a C2-5 alkylcarboxy anion, or a hydrogen carbonate anion; and
a is 2 when Y is a carbon atom and 3 when Y is a phosphorus atom.
- [8] A method for producing the divalent phosphazenium salt as defined in [2], characterized
by reacting at least 2 mol of an organic sulfonic acid to 1 mol of the phosphazenium
salt represented by the formula (5):

in the formula (5),
R1 and R2 represent each independently a hydrogen atom, a C1-20 hydrocarbon group, a ring structure in which R1 and R2 are bonded to each other, or a ring structure in which a plurality of R1 or R2 are bonded to each other; and
X- represents a hydroxy anion, a C1-4 alkoxy anion, a carboxy anion, a C2-5 alkylcarboxy anion, or a hydrogen carbonate anion.
- [9] A method for producing the divalent phosphazenium salt as defined in [3], characterized
by reacting at least 2 mol of an organic sulfonic acid to 1 mol of the phosphazenium
salt represented by the formula (6):

in the formula (6),
R1 and R2 represent each independently a hydrogen atom, a C1-20 hydrocarbon group, or a ring structure in which R1 and R2 are bonded to each other;
X- represents a hydroxy anion, a C1-4 alkoxy anion, a carboxy anion, a C2-5 alkylcarboxy anion, or a hydrogen carbonate anion.
- [10] A polyalkylene oxide composition characterized by comprising
the divalent phosphazenium salt as defined in any one of [1] to [5] and
a polyalkylene oxide.
- [11] The polyalkylene oxide composition according to [10], characterized in that when
measured by the following measuring method,
the amount of volatile acetaldehyde is at most 0.9 ppm, and
the amount of volatile propionaldehyde is at most 3.0 ppm,
[Measurement method]
- (I): 10 g of the sample is put in a container having an internal volume of 30 ml,
and
- (II): after (I), nitrogen bubbling is conducted at 0.5 L/min under heating at 65°C
for 2 hours to measure the amounts of volatilization.
- [12] The polyalkylene oxide composition according to [10] or [11], characterized in
that the pH of the polyalkylene oxide composition measured in accordance with the
method described in JIS K-1557-5 is at least 5 and at most 8.
- [13] A polyalkylene oxide composition characterized by comprising
the divalent phosphazenium salt as defined in [2], and
a polyalkylene oxide.
- [14] A polyurethane-forming composition comprising
- (A) the polyalkylene oxide composition as defined in any one of [10] to [13], and
- (B) an isocyanate compound.
- [15] A method for producing the polyalkylene oxide composition as defined in [13],
characterized in that
a polymerization reaction of an alkylene oxide is conducted in the presence of the
phosphazenium salt represented by the formula (5) and an active hydrogen-containing
compound to produce a polyalkylene oxide, and
then, at least 2 mol of an organic sulfonic acid is added to 1 mol of the phosphazenium
salt:

in the formula (5),
R1 and R2 represent each independently a hydrogen atom, a C1-20 hydrocarbon group, a ring structure in which R1 and R2 are bonded to each other, or a ring structure in which a plurality of R1 or R2 are bonded to each other; and
X- represents a hydroxy anion, a C1-4 alkoxy anion, a carboxy anion, a C2-5 alkylcarboxy anion, or a hydrogen carbonate anion.
ADVANTAGEOUS EFFECTS OF INVENTION
[0017] One embodiment of the present invention can provide a divalent phosphazenium salt
which is neutral and is excellent in heat stability and aldehyde scavenging ability,
and a method for producing the same.
[0018] Further, one embodiment of the present invention can provide a polyalkylene oxide
composition in which the amount of volatile aldehydes is reduced, and generation of
odor and turbidity is suppressed, and which is excellent in the urethane-forming reactivity.
Another embodiment of the present invention can provide a method for producing the
polyalkylene oxide composition. Yet another embodiment of the present invention can
provide a polyurethane-forming composition that contributes to formation of a polyurethane
having generation of odor and turbidity suppressed.
BRIEF DESCRIPTION OF DRAWINGS
[0019]
Fig. 1 is a diagram showing 1H-NMR of a phosphazenium salt-A obtained in Synthesis Example 1.
Fig. 2 is a diagram showing a change in pH during neutralization titration of the
phosphazenium salt-A obtained in Synthesis Example 1.
Fig. 3 is a diagram showing 1H-NMR of a phosphazenium salt-B obtained in Example 1.
Fig. 4 is a diagram showing 1H-NMR of a phosphazenium salt-C obtained in Comparative Example 1.
DESCRIPTION OF EMBODIMENTS
[0020] In the following, exemplary embodiments for carrying out the present invention will
be described in detail.
<Divalent phosphazenium salts>
[0021] The divalent phosphazenium salts according to one embodiment of the present invention
are divalent phosphazenium salts represented by the formulae (1) to (3):

in the formula (1),
R1 and R2 represent each independently a hydrogen atom, a C1-20 hydrocarbon group, a ring structure in which R1 and R2 are bonded to each other, or a ring structure in which a plurality of R1 or R2 are bonded to each other;
An- represents a deprotonated form of an organic sulfonic acid or organic disulfonic
acid;
either one of n and m is 1, and the other is 2; and
a is 2 when Y is a carbon atom and 3 when Y is a phosphorus atom.

in the formula (2),
R1 and R2 represent each independently a hydrogen atom, a C1-20 hydrocarbon group, a ring structure in which R1 and R2 are bonded to each other, or a ring structure in which a plurality of R1 or R2 are bonded to each other; and
A- represents a deprotonated form of an organic sulfonic acid.

in the formula (3),
R1 and R2 represent each independently a hydrogen atom, a C1-20 hydrocarbon group, or a ring structure in which R1 and R2 are bonded to each other,
An- represents a deprotonated form of an organic sulfonic acid or organic disulfonic
acid; and
either one of n and m is 1 and the other is 2.
[0022] The divalent phosphazenium salts according to this embodiment may be any salts so
long as they belong to the scopes of the salts represented by the above formulae (1)
to (3).
<<<R1, R2>>>
[0023] In the formulae (1) to (3), R
1 and R
2 represent each independently a hydrogen atom, a C
1-20 hydrocarbon group, a ring structure in which R
1 and R
2 are bonded to each other, or a ring structure in which a plurality of R
1 or R
2 are bonded to each other.
[0024] The C
1-20 hydrocarbon group may, for example, be a methyl group, an ethyl group, a vinyl group,
a n-propyl group, an isopropyl group, a cyclopropyl group, an allyl group, a n-butyl
group, an isobutyl group, a t-butyl group, a cyclobutyl group, a n-pentyl group, a
neopentyl group, a cyclopentyl group, a n-hexyl group, a cyclohexyl group, a phenyl
group, a heptyl group, a cycloheptyl group, an octyl group, a cyclooctyl group, a
nonyl group, a cyclononyl group, a decyl group, a cyclodecyl group, an undecyl group,
a dodecyl group, a tridecyl group, a tetradecyl group, a pentadecyl group, a hexadecyl
group, a heptadecyl group, an octadecyl group, a nonadecyl group, etc.
[0025] The ring structure in which R
1 and R
2 are bonded to each other, may be a pyrrolidinyl group, a pyrrolyl group, a piperidinyl
group, an indolyl group, an isoindolyl group, etc.
[0026] In the formulae (1) and (2), the ring structure in which a plurality of R
1 or R
2 are bonded to each other, may, for example, be a ring structure in which two R
1 or two R
2 become each independently one group selected from alkylene groups such as a methylene
group, an ethylene group, a propylene group, a butylene group, etc. and one alkylene
group and the other alkylene group are bonded to each other.
[0027] Among these, from the viewpoint of easy availability of guanidines as the raw material,
it is preferred that R
1 and R
2 are each independently a methyl group, an ethyl group or an isopropyl group. It is
more preferred that R
1 and R
2 are methyl groups.
[0028] Specific examples of the cation species in the formulae (1) and (2) include tetrakis(1,1,3,3-tetramethylguanidino)phosphonium(hydro)dication,
tetrakis(1,1,3,3-tetraethylguanidino)phosphonium(hydro)dication, tetrakis(1,1,3,3-tetra(n-propyl)guanidino)phosphonium(hydro)dication,
tetrakis(1,1,3,3-tetraisopropylguanidino)phosphonium(hydro)dication, tetrakis(1,1,3,3-tetra(n-butyl)guanidino)phosphonium(hydro)dication,
tetrakis(1,1,3,3-tetraphenylguanidino)phosphonium(hydro)dication, tetrakis(1,1,3,3-tetrabenzylguanidino)phosphonium(hydro)dication,
tetrakis(1,3-dimethylimidazolidin-2-imino)phosphonium(hydro)dication, and tetrakis(1,3-diethylimidazolidin-2-imino)phosphonium(hydro)dication.
Among them, tetrakis(1,1,3,3-tetramethylguanidino)phosphonium(hydro)dication is preferred.
[0029] Specific examples of the cation species in the formulae (1) and (3) include tetrakis[tris(dimethylamino)phosphoranylideneamino]phosphonium(hydro)dication,
tetrakis[tris(diethylamino)phosphoranylideneamino]phosphonium(hydro)dication, tetrakis[tris(di-n-propylamino)phosphoranylideneamino]phosphonium(hydro)dication,
tetrakis[tris(diisopropylamino)phosphoranylideneamino]phosphonium(hydro)dication,
tetrakis[tris(di-n-butylamino)phosphoranylideneamino]phosphonium(hydro)dication, tetrakis[tris(diphenylamino)phosphoranylideneamino]phosphonium(hydro)dication,
tetrakis[tris(dibenzylamino)phosphoranylideneamino]phosphonium(hydro)dication, tetrakis[tris(dipyrrolidinylamino)phosphoranylideneamino]phosphonium(hydro)dication,
and tetrakis[tris(dipyrrolylamino)phosphoranylideneamino]phosphonium(hydro)dication.
Among them, tetrakis[tris(dimethylamino)phosphoranylideneamino]phosphonium (hydro)dication
is preferred.
<<A- and An->>
[0030] In the formulae (1) to (3), A
- represents a deprotonated form of an organic sulfonic acid. A
n- represents a deprotonated form of an organic sulfonic acid or organic disulfonic
acid. In a case where, instead of an organic sulfonic acid, an inorganic acid such
as hydrochloric acid, perchloric acid, sulfuric acid, sulfurous acid or nitric acid;
or an organic carboxylic acid such as acetic acid, adipic acid, benzoic acid or oxalic
acid; is used, the phosphazenium salt will precipitate from inside the polyalkylene
oxide, whereby the polyalkylene oxide composition becomes cloudy, and an odor derived
from the acid is likely to be generated, such being undesirable.
[0031] As the organic sulfonic acid and organic disulfonic acid, any organic sulfonic acid
and organic disulfonic acid may be used so long as they belong to the scopes of generally
known organic sulfonic acids and organic disulfonic acids.
[0032] The organic sulfonic acid may, for example, be an alkane sulfonic acid, an α-olefin
sulfonic acid, a higher alcohol sulfuric acid, a polyoxyethylene alkyl ether sulfuric
acid or the like.
[0033] The organic disulfonic acid may, for example, be an alkane disulfonic acid, an α-olefin
disulfonic acid, a higher alcohol disulfuric acid, a polyoxyethylene alkyl ether disulfuric
acid or the like.
[0034] Specific examples of the organic sulfonic acid and organic disulfonic acid include,
for example, p-toluenesulfonic acid, xylenesulfonic acid, cumenesulfonic acid, methoxybenzenesulfonic
acid, dodecylbenzenesulfonic acid, a linear alkylbenzenesulfonic acid (soft type),
a branched chain alkylbenzenesulfonic acid (hard type), an alkyl diphenyl ether disulfonic
acid, a linear alkyl naphthalene sulfonic acid, a branched chain alkyl naphthalene
sulfonic acid, a β-naphthalene sulfonic acid formalin condensate, p-aniline sulfonic
acid, o-aniline sulfonic acid, etc. Among them, from the viewpoint of industrial availability
and being excellent in stability of the phosphazenium salt and in aldehyde scavenging
effect, dodecylbenzenesulfonic acid, a linear alkylbenzenesulfonic acid (soft type),
or a branched chain alkylbenzenesulfonic acid (hard type), is preferred.
[0035] In the formulae (1) and (3), either one of n and m is 1 and the other is 2. That
is, when n is 1, m is 2, and when n is 2, m is 1.
[0036] As the combination of R
1 and R
2 with A
n- or A
-, from such a viewpoint that guanidines as the raw material are readily available,
and being excellent in the stability of the phosphazenium salt and in aldehyde scavenging
effect, it is preferred that R
1 and R
2 are methyl groups, and A
n- or A
- is a deprotonated form of dodecylbenzenesulfonic acid, a linear alkylbenzenesulfonic
acid (soft type) or a branched chain alkylbenzenesulfonic acid (hard type).
[0037] The divalent phosphazenium salt according to this embodiment preferably exhibits
neutrality. At the time when the divalent phosphazenium salt is added to e.g. a resin
or the like, a change in pH of the resin or the like will be suppressed. The pH of
a 0.01 mol/L aqueous solution of the divalent phosphazenium salt is preferably at
least 5 and at most 9, more preferably at least 5 and at most 8. The pH can be measured,
for example, by attaching a 0.01 mol/L aqueous solution of the divalent phosphazenium
salt to a pH test paper.
[0038] The phosphazenium salt according to this embodiment is excellent in thermal stability.
The divalent phosphazenium salt has no or almost no odor when subjected to heat treatment
at 120°C for 8 hours, and has no or almost no change in purity when measured by means
of an NMR (nuclear magnetic resonance) apparatus.
[0039] The divalent phosphazenium salt according to this embodiment can be used as an aldehyde
scavenger. For example, by adding any one of the phosphazenium salts represented by
the above formulae (1) to (3) to a polyalkylene oxide, the amount of aldehyde volatilized
from the polyalkylene oxide can be reduced.
<Method for producing divalent phosphazenium salt>
[0040] A method for producing a divalent phosphazenium salt according to one embodiment
of the present invention is a method for producing a divalent phosphazenium salt represented
by one of the above formulae (1) to (3), characterized by reacting at least 2 mol
of an organic sulfonic acid to 1 mol of a phosphazenium salt represented by the formula
(4):

in the formula (4),
R1 and R2 represent each independently a hydrogen atom, a C1-20 hydrocarbon group, a ring structure in which R1 and R2 are bonded to each other, or a ring structure in which a plurality of R1 or R2 are bonded to each other;
X- represents a hydroxy anion, a C1-4 alkoxy anion, a carboxy anion, a C2-5 alkylcarboxy anion, or a hydrogen carbonate anion; and
a is 2 when Y is a carbon atom and 3 when Y is a phosphorus atom.
[0041] The method for producing a divalent phosphazenium salt according to one embodiment
of the present invention is the method for producing a divalent phosphazenium salt
represented by the above formula (2), characterized by reacting at least 2 mol of
an organic sulfonic acid to 1 mol of the phosphazenium salt represented by the formula
(5):

in the formula (5),
R1 and R2 represent each independently a hydrogen atom, a C1-20 hydrocarbon group, a ring structure in which R1 and R2 are bonded to each other, or a ring structure in which a plurality of R1 or R2 are bonded to each other; and
X- represents a hydroxy anion, a C1-4 alkoxy anion, a carboxy anion, a C2-5 alkylcarboxy anion, or a hydrogen carbonate anion.
[0042] The method for producing a divalent phosphazenium salt according to one embodiment
of the present invention is the method for producing a divalent phosphazenium salt
represented by the above formula (3), characterized by reacting at least 2 mol of
an organic sulfonic acid to 1 mol of the phosphazenium salt represented by the formula
(6):

in the formula (6),
R1 and R2 represent each independently a hydrogen atom, a C1-20 hydrocarbon group, or a ring structure in which R1 and R2 are bonded to each other; and
X- represents a hydroxy anion, a C1-4 alkoxy anion, a carboxy anion, a C2-5 alkylcarboxy anion, or a hydrogen carbonate anion.
<<<R1, R2>>>
[0043] In the formulae (4) to (6), R
1 and R
2 are each independently a hydrogen atom, a C
1-20 hydrocarbon group, a ring structure in which R
1 and R
2 are bonded to each other, or a ring structure in which a plurality of R
1 or R
2 are bonded to each other. Specific examples thereof may be the same ones as R
1 and R
2 in the above formulae (1) to (3). And like in the above formulae (1) to (3), from
the viewpoint of easy availability of the guanidines as the raw material, as R
1 and R
2, a methyl group, an ethyl group, or an isopropyl group, is preferred.
[0044] Specific examples of the monovalent phosphazenium salts represented by the formulae
(4) and (5) include tetrakis(1,1,3,3-tetramethylguanidino)phosphonium hydroxide, tetrakis(1,1,3,3-tetraethylguanidino)phosphonium
hydroxide, tetrakis(1,1,3,3-tetra(n-propyl)guanidino)phosphonium hydroxide, tetrakis(1,1,3,3-tetraisopropylguanidino)phosphonium
hydroxide, tetrakis(1,1,3,3-tetra(n-butyl)guanidino)phosphonium hydroxide, tetrakis(1,1,3,3-tetraphenylguanidino)phosphonium
hydroxide, tetrakis(1,1,3,3-tetrabenzylguanidino)phosphonium hydroxide, tetrakis(1,3-dimethylimidazolidin-2-imino)phosphonium
hydroxide, tetrakis(1,3-diethylimidazolidin-2-imino)phosphonium hydroxide; tetrakis(1,1,3,3-tetramethylguanidino)phosphonium
hydrogen carbonate, tetrakis(1,1,3,3-tetraethylguanidino)phosphonium hydrogen carbonate,
tetrakis(1,1,3,3-tetra(n-propyl)guanidino)phosphonium hydrogen carbonate, tetrakis(1,1,3,3-tetraisopropylguanidino)phosphonium
hydrogen carbonate, tetrakis(1,1,3,3-tetra(n-butyl)guanidino)phosphonium hydrogen
carbonate, tetrakis(1,1,3,3-tetraphenylguanidino)phosphonium hydrogen carbonate, tetrakis(1,1,3,3-tetrabenzylguanidino)phosphonium
hydrogen carbonate, tetrakis(1,3-dimethylimidazolidin-2-imino)phosphonium hydrogen
carbonate, tetrakis(1,3-diethylimidazolidin-2-imino)phosphonium hydrogen carbonate,
etc. Among them, from the viewpoint of the availability of guanidines as the raw material,
tetrakis(1,1,3,3-tetramethylguanidino)phosphonium hydroxide is preferred.
[0045] Specific examples of the monovalent phosphazenium salts represented by the formulae
(4) and (6) include tetrakis[tris(dimethylamino)phosphoranylideneamino]phosphonium
hydroxide, tetrakis[tris(diethylamino)phosphoranylideneamino]phosphonium hydroxide,
tetrakis[tris(di-n-propylamino)phosphoranylideneamino]phosphonium hydroxide, tetrakis[tris(diisopropylamino)phosphoranylideneamino]phosphonium
hydroxide, tetrakis[tris(di-n-butylamino)phosphoranylideneamino]phosphonium hydroxide,
tetrakis[tris(diphenylamino)phosphoranylideneamino]phosphonium hydroxide, tetrakis[tris(dibenzylamino)phosphoranylideneamino]phosphonium
hydroxide, tetrakis[tris(dipyrrolidinylamino)phosphoranylideneamino]phosphonium hydroxide,
tetrakis[tris(dipyrrolylamino)phosphoranylideneamino]phosphonium hydroxide; tetrakis[tris(dimethylamino)phosphoranylideneamino]phosphonium
hydrogen carbonate, tetrakis[tris(diethylamino)phosphoranylideneamino]phosphonium
hydrogen carbonate, tetrakis[tris(di-n-propylamino)phosphoranylideneamino]phosphonium
hydrogen carbonate, tetrakis[tris(diisopropylamino)phosphoranylideneamino]phosphonium
hydrogen carbonate, tetrakis[tris(di-n-butylamino)phosphoranylideneamino]phosphonium
hydrogen carbonate, tetrakis[tris(diphenylamino)phosphoranylideneamino]phosphonium
hydrogen carbonate, tetrakis[tris(dibenzylamino)phosphoranylideneamino]phosphonium
hydrogen carbonate, tetrakis[tris(dipyrrolidinylamino)phosphoranylideneamino]phosphonium
hydrogen carbonate, tetrakis[tris(dipyrrolylamino)phosphoranylideneamino]phosphonium
hydrogen carbonate; etc. Among them, from the viewpoint of easy availability of raw
materials, tetrakis[tris(dimethylamino)phosphoranylideneamino]phosphonium hydroxide
and tetrakis[tris(dimethylamino)phosphoranylideneamino]phosphonium hydrogen carbonate
are preferred.
[0046] The amount of the organic sulfonic acid to 1 mol of the monovalent phosphazenium
salt represented by one of the formulae (4) to (6) is at least 2 mol, preferably at
least 2.1 mol and at most 10 mol, more preferably at least 2.2 mol and at most 5 mol.
If the amount of the organic sulfonic acid is less than 2 mol to 1 mol of the monovalent
phosphazenium salt, the obtainable phosphazenium salt will be unstable, and the purity
may decrease, such being undesirable.
[0047] The reaction between the monovalent phosphazenium salt represented by one of the
formulae (4) to (6) and the organic sulfonic acid may be carried out in a solvent.
As the solvent, water; an alcohol such as methanol, ethanol, n-propanol, isopropanol,
n-butanol, isobutanol, t-butanol, n-pentanol, neopentanol, n-hexanol, n-heptanol,
n-octanol, n-nonanol or n-decanol; a polyhydric alcohol such as diethylene glycol,
triethylene glycol, propylene glycol, 1,3-butanediol, 1,4-butanediol, 2,3-butanediol
or glycerin; a polyhydric alcohol derivative such as ethylene glycol monomethyl ether,
ethylene glycol monoethyl ether, ethylene glycol monobenzyl ether or ethylene glycol
monophenyl ether; a fatty acid such as formic acid or acetic acid; or a nitrogen-containing
compound such as ethylenediamine, aniline or acetonitrile, may be mentioned. As the
solvent, one type may be used alone, or a mixed solvent of two or more types may be
used.
[0048] The phosphazenium salt according to one embodiment of the present invention is neutral
and excellent in thermal stability, and further has an aldehyde scavenging effect.
Therefore, at the time when the divalent phosphazenium salt is added to, for example,
a polyalkylene oxide, it is possible to capture an aldehyde in the polyalkylene oxide
while keeping the polyalkylene oxide neutral.
<Polyalkylene oxide composition>
[0049] A polyalkylene oxide composition according to one embodiment of the present invention
contains the divalent phosphazenium salt represented by one of the above formulae
(1) to (3) and a polyalkylene oxide.
«Polyalkylene oxide»
[0050] As the polyalkylene oxide, any polyalkylene oxide may be used so long as it belongs
to the scope generally known as a polyalkylene oxide. For example, polyethylene oxide,
polypropylene oxide, poly(1,2-butylene oxide), poly(2,3-butylene oxide), polyisobutylene
oxide, polybutadiene oxide, polypentene oxide, polycyclohexene oxide, polystyrene
oxide, etc. may be mentioned. Further, a block copolymer and a random copolymer containing
these as copolymerization components may be mentioned. Among these, polyethylene oxide,
polypropylene oxide, and a polypropylene oxide-polyethylene oxide block copolymer
are preferred.
[0051] In the polyalkylene oxide composition, the content of the divalent phosphazenium
salt is not particularly limited, but since it is possible to obtain a polyalkylene
oxide composition in which odor and turbidity are suppressed and the amount of volatile
aldehyde is small, it is preferably at least 50 ppm and at most 10,000 ppm, more preferably
at least 100 ppm and at most 5,000 ppm, further preferably at least 200 ppm and at
most 3,000 ppm.
[0052] The polyalkylene oxide composition may contain an antioxidant. The antioxidant may,
for example, be a phenolic antioxidant such as 2,6-di-tert-butyl-4-methylphenol, 2-tert-butyl-4-methoxyphenol,
2,6-di-tert-butylphenol, 6-tert-butyl-2,4-methylphenol, pentaerythritol tetrakis[3-(3,5-di-tert-butyl-4-hydroxyphenylpropionate]
(e.g. Irganox 1010 manufactured by BASF), 3,5-bis-tert-butyl-4-hydroxybenzenepropanoic
acid octadecyl ester (e.g. Irganox 1076 manufactured by BASF) or 3,5-bis-tert-butyl-4-hydroxybenzenepropanoic
acid isooctyl ester (e.g. Irganox 1135 manufactured by BASF); or an amine-type antioxidant
such as n-butyl-p-aminophenol, 4,4-dimethyldiamine or 4,4-dioctyldiphenylamine. These
antioxidants may be used alone or in combination of two or more.
[0053] The polyalkylene oxide composition according to this embodiment is one having generation
of odor suppressed. The polyalkylene oxide composition is one which has no odor or
substantially no odor at the time when 10 g of the polyalkylene oxide composition
is put in a 20 ml sample tube, left to stand still for 12 hours in the sealed state
and then opened.
[0054] The polyalkylene oxide composition according to this embodiment is one having occurrence
of turbidity suppressed. The polyalkylene oxide composition is one which has no turbidity
or substantially no turbidity at the time when 10 g of the polyalkylene oxide composition
is put in a 20 ml sample tube and visually observed.
[0055] The polyalkylene oxide composition according to this embodiment is excellent in urethanization
reactivity. The polyalkylene oxide composition is preferably one, of which the pH
as measured in accordance with the method described in JIS K-1557-5 is at least 5
and at most 8. When the pH is at least 5 and at most 8, the reactivity at the time
when the polyalkylene oxide composition and the isocyanate compound are mixed to synthesize
a polyurethane-forming composition, will be further improved, such being preferred.
[0056] The polyalkylene oxide composition according to this embodiment has little volatile
aldehydes. As the index in the present embodiment, the amount of acetaldehyde to be
volatilized by nitrogen bubbling (flow rate: 0.5 L/min) under heating at constant
conditions (65°C, 2 hours) is preferably at most 0.9 ppm, more preferably at most
0.8 ppm. Further, the amount of propionaldehyde to be volatilized under the above
conditions is preferably at most 3.0 ppm, more preferably at most 2.5 ppm.
[0057] The polyalkylene oxide composition according to this embodiment has little volatile
aldehydes. As the index in the present embodiment, when measured by the following
measurement method,
the amount of volatile acetaldehyde is preferably at most 0.9 ppm, and
the amount of volatile propionaldehyde is preferably at most 3.0 ppm:
[Measurement method]
- (I): 10 g of the sample is put in a container having an internal volume of 30 ml,
and
- (II): after (I), nitrogen bubbling is conducted at 0.5 L/min under heating at 65°C
for 2 hours to measure the amounts of volatilization.
[0058] More specifically, when measured in the order of the following (i) to (iv), the amount
of volatile acetaldehyde is preferably at most 0.9 ppm, more preferably at most 0.8
ppm. Further, when measured in the order of the following (i) to (iv), the amount
of volatile propionaldehyde is preferably at most 3.0 ppm, more preferably at most
2.5 ppm.
- (i) The polyalkylene oxide composition is put in an impinger having an internal capacity
of 30 ml, and under heating at constant conditions (65°C, 2 hours), subjected to bubbling
at 65°C with nitrogen through a hydrocarbon trap (flow rate: 0.5 L/min),
- (ii) the volatilized gas is collected in a 2,4-dinitrophenylhydrazine (DNPH) cartridge,
- (iii) using 5 ml of an eluent, the adsorbed component is eluted, and
- (iv) high speed liquid chromatography (high performance liquid chromatography) measurement
is carried out.
<Method for producing polyalkylene oxide composition>
[0059] As a method for producing a polyalkylene oxide composition containing the phosphazenium
salt represented by the formula (1) or (3) and a polyalkylene oxide, any method may
be used so long as it is a method which can produce a polyalkylene oxide composition
containing the divalent phosphazenium salt represented by the above formula (1) or
(3) and a polyalkylene oxide. For example, a method of mixing the divalent phosphazenium
salt represented by the above formula (1) or (3) with a polyalkylene oxide may be
mentioned. The temperature at which the phosphazenium salt is mixed with the polyalkylene
oxide may be any temperature, and, for example, a range of from 40 to 130°C may be
mentioned.
[0060] As a method for producing a polyalkylene oxide composition containing a divalent
phosphazenium salt represented by the formula (2) and a polyalkylene oxide, any method
may be used so long as it is a method which can produce a polyalkylene oxide composition
containing the divalent phosphazenium salt represented by the above formula (2) and
a polyalkylene oxide. For example, a method of mixing the divalent phosphazenium salt
represented by the above formula (2) with a polyalkylene oxide may be mentioned. Further,
a method may be mentioned in which in the presence of the monovalent phosphazenium
salt represented by the above formula (5) and an active hydrogen-containing compound,
ring-opening polymerization of an alkylene oxide is carried out to produce a polyalkylene
oxide, and then, at least 2 mol of an organic sulfonic acid is added to 1 mol of the
phosphazenium salt.
[0061] A method for producing a polyalkylene oxide composition according to one embodiment
of the present invention is the above method for producing a polyalkylene oxide composition,
in which in the presence of the phosphazenium salt represented by the formula (5)
and an active hydrogen-containing compound, a polymerization reaction of an alkylene
oxide is carried out to produce a polyalkylene oxide, and then, at least 2 mol of
an organic sulfonic acid is added to 1 mol of the phosphazenium salt:

in the formula (5),
R1 and R2 represent each independently a hydrogen atom, a C1-20 hydrocarbon group, a ring structure in which R1 and R2 are bonded to each other, or a ring structure in which a plurality of R1 or R2 are bonded to each other; and
X- represents a hydroxy anion, a C1-4 alkoxy anion, a carboxy anion, a C2-5 alkylcarboxy anion, or a hydrogen carbonate anion.
[0062] The alkylene oxide may, for example, be a C
2-20 alkylene oxide. Specifically, ethylene oxide, propylene oxide, 1,2-butylene oxide,
2,3-butylene oxide, isobutylene oxide, butadiene monooxide, pentene oxide, styrene
oxide, cyclohexene oxide, etc. may be mentioned. Among them, ethylene oxide or propylene
oxide is preferred because the alkylene oxide is easily available and the obtained
polyalkylene oxide has high industrial value. As the alkylene oxide, one type may
be used alone, or two or more types may be used in combination. When two or more types
are used as mixed, for example, the first alkylene oxide may be reacted and then the
second alkylene oxide may be reacted, or two or more types of alkylene oxide may be
simultaneously reacted.
[0063] The active hydrogen-containing compound may be a hydroxy compound, an amine compound,
a carboxylic acid compound, a thiol compound, a polyether polyol having a hydroxy
group, etc.
[0064] The hydroxy compound may, for example, be water, ethylene glycol, diethylene glycol,
propylene glycol, dipropylene glycol, 1,3-propanediol, 1,3-butanediol, 1,4-butanediol,
1,6-hexanediol, glycerin, trimethylolpropane, hexanetriol, pentaerythritol, diglycerin,
sorbitol, sucrose, glucose, 2-naphthol, bisphenol, etc.
[0065] The amine compound may, for example, be ethylenediamine, N,N'-dimethylethylenediamine,
piperidine, piperazine, etc.
[0066] The carboxylic acid compound may, for example, be benzoic acid, adipic acid, etc.
[0067] The thiol compound may, for example, be ethanedithiol, butanedithiol, etc.
[0068] The polyether polyol having a hydroxy group may, for example, be a polyether polyol
having a hydroxy group, such as a polyether polyol having a molecular weight of from
200 to 3,000.
[0069] These active hydrogen-containing compounds may be used alone or in combination of
a few types as mixed.
[0070] As the organic sulfonic acid, the same one as the organic sulfonic acid mentioned
in the above formula (2) may be mentioned.
[0071] In a case where, in place of the organic sulfonic acid, an inorganic acid such as
hydrochloric acid, perchloric acid, sulfuric acid, sulfurous acid or nitric acid;
or an organic carboxylic acid such as acetic acid, adipic acid, benzoic acid or oxalic
acid, is used, the phosphazenium salt will precipitate from inside of the polyalkylene
oxide composition, whereby the polyalkylene oxide composition becomes cloudy, and
an odor derived from an acid is likely to be generated, such being undesirable.
[0072] The amount of the organic sulfonic acid to be added is at least 2 mol, preferably
at least 2 mol and at most 10 mol, more preferably at least 2.1 mol and at most 8
mol, further preferably at least 2.2 mol and at most 5.0 mol, to 1 mol of the phosphazenium
salt represented by the above formula (5). If it is less than 2 mol, an unreacted
monovalent phosphazenium salt will remain, and an odor will be generated in the polyalkylene
oxide composition, such being undesirable. On the other hand, when the amount is at
most 10 mol, the polyalkylene oxide composition will exhibit good liquidity (pH) and
will be excellent in urethanization reactivity, such being preferred.
<Polyurethane-forming composition>
[0073] A polyurethane-forming composition according to one embodiment of the present invention
comprises:
- (A) a polyalkylene oxide composition containing the divalent phosphazenium salt represented
by one of the above formulae (1) to (3) and a polyalkylene oxide, and
- (B) an isocyanate compound.
[0074] The isocyanate compound (B) may be any one so long as it is one belonging to the
scope generally known as an isocyanate compound, and, for example, an aromatic isocyanate
compound, an aliphatic isocyanate compound, an alicyclic isocyanate compound, and
polyisocyanate derivatives thereof, may be mentioned.
[0075] The aromatic isocyanate compound may, for example, be tolylene diisocyanate (2,4-
or 2,6-tolylene diisocyanate or a mixture thereof) (TDI), phenylene diisocyanate (m-
or p-phenylene diisocyanate, or a mixture thereof), 4,4'-diphenyl diisocyanate, diphenylmethane
diisocyanate (4,4'-, 2,4'- or 2,2'-diphenylmethane diisocyanate, or a mixtures thereof)
(MDI), 4,4'-toluidine diisocyanate (TODI), 4,4'-diphenyl ether diisocyanate, xylylene
diisocyanate (1,3- or 1,4-xylylene diisocyanate, or a mixture thereof) (XDI), tetramethylxylylene
diisocyanate (1,3- or 1,4-tetramethylxylylene diisocyanate or a mixture thereof) (TMXDI),
ω,ω'-diisocyanate-1,4-diethylbenzene, naphthalene diisocyanate (1,5-, 1,4- or 1,8-naphthalene
diisocyanate or a mixture thereof) (NDI), triphenylmethane triisocyanate, tris(isocyanatephenyl)
thiophosphate, polymethylene polyphenylene polyisocyanate, nitrodiphenyl-4,4'-diisocyanate,
3,3'-dimethyldiphenylmethane-4,4'-diisocyanate, 4,4'-diphenylpropane diisocyanate,
3,3'-dimethoxydiphenyl-4,4'-diisocyanate, etc.
[0076] The aliphatic isocyanate compound may, for example, be trimethylene diisocyanate,
1,2-propylene diisocyanate, butylene diisocyanate (tetramethylene diisocyanate, 1,2-butylene
diisocyanate, 2,3-butylene diisocyanate, or 1,3-butylene diisocyanate), hexamethylene
diisocyanate, pentamethylene diisocyanate, 2,2,4-trimethylhexamethylene diisocyanate,
2,4,4-trimethylhexamethylene diisocyanate, 2,6-diisocyanate methylcapate, lysine diisocyanate,
lysine ester triisocyanate, 1,6,11-undecane triisocyanate, 1,3,6-hexamethylene triisocyanate,
trimethylhexamethylene diisocyanate, decamethylene diisocyanate., etc.
[0077] The alicyclic isocyanate compound may, for example, be a monocyclic alicyclic isocyanate
compound such as 1,3-cyclopentane diisocyanate, 1,3-cyclopentene diisocyanate, cyclohexane
diisocyanate (1,4-cyclohexane diisocyanate, or 1,3-cyclohexane diisocyanate), 3-isocyanate
methyl-3,5,5-trimethylcyclohexyl isocyanate (isophorone diisocyanate, IPDI), methylene
bis(cyclohexyl isocyanate (4,4'-, 2,4'- or 2,2'-methylene bis(cyclohexyl isocyanate,
or a mixture thereof) (hydrogenated MDI), methylcyclohexanediisocyanate (methyl-2,4-cyclohexanediisocyanate,
methyl-2,6-cyclohexanediisocyanate, bis(isocyanatemethyl)cyclohexane (1,3- or 1,4-bis(isocyanatemethyl)cyclohexane,
or a mixture thereof) (hydrogenated XDI), dimer acid diisocyanate, transcyclohexane
1,4-diisocyanate, hydrogenated tolylene diisocyanate (hydrogenated TDI), or hydrogenated
tetramethylxylylene diisocyanate (hydrogenated TMXDI); a cyclic alicyclic isocyanate
compound such as norbornene diisocyanate, norbornane diisocyanate methyl, bicycloheptane
triisocyanate, diisocyanatomethyl bicycloheptane, or di(diisocyanatomethyl)tricyclodecane;
etc.
[0078] Further, the derivatives of these polyisocyanates may, for example, be multimers
of the above isocyanate compounds (dimers, trimers, pentamers, heptamers, uretidinediones,
ureytonimines, isocyanurate modified products, polycarbodiimides, etc.), a urethane
modified product (for example, a urethane modified product obtained by modifying or
reacting a part of the isocyanate groups in the isocyanate compound or the multimer
with a monool or a polyol), a biuret modified product (for example, a biuret modified
product produced by reacting the above isocyanate compound with water), an allophanate
modified product (for example, an allophanate modified product produced by a reaction
of the above isocyanate compound with a monool or polyol component), an urea modified
product (for example, an urea modified product produced by a reaction of the above
isocyanate compound with a diamine), an oxadiazinetrione (for example, an oxadiazinetrione
produced by a reaction of the above isocyanate compound with carbon dioxide gas),
etc.
[0079] Here, as the above isocyanate compound or its derivative, one type may be used alone,
or two or more types may be used in combination.
[0080] The polyurethane-forming composition may contain various additives. With the polyurethane-forming
composition containing additives, the effects of the additives are expected.
[0081] As the additives, a catalyst, a foam stabilizer, a cross-linking agent, a communicating
agent, a foaming agent, a dye, an organic pigment, an inorganic pigment, an inorganic
reinforcing material, a plasticizer, a processing aid, an ultraviolet absorber, a
light stabilizer, a lubricant, a wax, a crystal nucleating agent, a release agent,
a hydrolysis inhibitor, an antifogging agent, a dustproofing agent, a rustproofing
agent, an ion trap agent, a flame retardant, a flame retardant aid, an inorganic filler,
an organic filler, etc. may be mentioned.
EXAMPLES
[0082] In the following, the respective embodiments of the present invention will be described
with reference to Examples, but these Examples do not limit the respective embodiments
of the present invention. First, the evaluation/measurement methods used in Examples
and Comparative Examples will be shown.
(1) NMR of phosphazenium salt
[0083] 1H-NMR was measured using a nuclear magnetic resonance (NMR) spectrum measuring device
(manufactured by JEOL Ltd., (trade name) GSX270WB) using deuterated chloroform as
a heavy solvent.
(2) pH of phosphazenium salt
[0084] A 0.01 mol/L phosphazenium salt aqueous solution was attached to a pH test paper,
and the pH of the phosphazenium salt was measured.
(3) pH of polyalkylene oxide
[0085] In accordance with the method described in JIS K-1557-5, 10 g of a polyalkylene oxide
was dissolved in a mixed solvent (60 mL) of isopropanol/water = 10/6, and using a
pH/ORP meter PH72 manufactured by YOKOGAWA, the pH of the polyalkylene oxide was measured.
(4) Amounts of aldehydes votatilized from polyalkylene oxide
[0086] 10 g of a polyalkylene oxide was put in an impinger (manufactured by Suenaga Rikagaku
Co., Ltd., capacity: 30 ml), and while heating at 65°C for 2 hours, nitrogen gas aerated
with a hydrocarbon trap was blown in at 65°C at a flow rate of 0.5 L/min. The gas
after aeration was collected in a 2,4-dinitrophenylhydrazine (DNPH) cartridge, and
using 5 ml of an eluent, the adsorbed component was eluted. The eluate was measured
by high performance liquid chromatography (HPLC) to measure the amounts of aldehydes
volatilized from the polyalkylene oxide.
(5) Hydroxyl value of polyalkylene oxide (unit: mgKOH/g)
[0087] Calculated by the method described in JIS K-1557-1.
(6) Odor of polyalkylene oxide composition
[0088] 10 g of a polyalkylene oxide composition was put in a 20 ml sample tube, left for
12 hours in a sealed state, and then opened to evaluate the presence or absence of
odor.
(7) Turbidity of polyalkylene oxide
[0089] 10 g of a polyalkylene oxide composition was put in a 20 ml sample tube and visually
observed, whereby the presence or absence of turbidity was evaluated.
(8) Odor of polyurethane-forming composition
[0090] A polyurethane-forming composition immediately after the production was put in a
sample bottle and left to stand still for 1 hour in a sealed state. At the time when
opened, the presence or absence of odor was evaluated.
<Synthesis Example 1>
[0091] A 2 L four-necked flask equipped with a stirring blade was made to be under a nitrogen
atmosphere, and 96 g (0.46 mol) of phosphorus pentachloride and 800 ml of dehydrated
toluene were added and stirred at 20°C. While maintaining stirring, 345 g (2.99 mol)
of 1,1,3,3-tetramethylguanidine was added dropwise over 3 hours, then the temperature
was raised to 100°C, and further 107 g (0.92 mol) of 1,1,3,3-tetramethylguanidine
was added dropwise over 1 hour. The obtained white slurry solution was stirred at
100°C for 14 hours and then cooled to 80°C, and 250 ml of ion-exchanged water was
added and further stirred for 30 minutes. When the stirring was stopped, the slurry
had been completely dissolved, and a two-phase solution was obtained. The obtained
two-phase solution was separated into oil and water, and the aqueous phase was recovered.
To the obtained aqueous phase, 100 ml of dichloromethane was added to conduct oil-water
separation, whereupon the dichloromethane phase was recovered. The obtained dichloromethane
solution was washed with 100 ml of deionized water.
[0092] The obtained dichloromethane solution was transferred to a 2 L four-necked flask
equipped with a stirring blade, 900 g of 2-propanol was added, and then the temperature
was raised to 80 to 100°C under normal pressure to remove dichloromethane. The obtained
2-propanol solution was allowed to cool to an internal temperature of 60°C with stirring,
and then, 31 g (0.47 mol) of 85 mass% potassium hydroxide was added and reacted at
60°C for 2 hours. The temperature was cooled to 25°C, and the precipitated by-product
salt was removed by filtration to obtain 860 g of a 2-propanol solution of monovalent
phosphazenium salt-A at a concentration of 25 mass% in a yield of 92%. The phosphazenium
salt-A is a phosphazenium salt corresponding to the above formula (5) in which R
1 is a methyl group, R
2 is a methyl group, and X
- is a hydroxy anion. The pH of the obtained phosphazenium salt-A was 12 (basic).
[0093] Then,
1H-NMR of the obtained phosphazenium salt-A was measured.
[0094] Fig. 1 is a diagram showing
1H-NMR of the phosphazenium salt-A obtained in Synthesis Example 1.
1.21 (d, 72H, methyl group of 2-propanol), 2.83 (s, 48H, methyl group of monovalent
phosphazenium salt), 4.02 (sep, 12H, methine of 2-propanol).
[0095] Further, the phosphazenium salt-A was subjected to heat treatment at 120°C for 8
hours, and as a result, a strong odor was generated, and formation of an impurity
peak was confirmed by
1H-NMR.
<Synthesis Example 2>
[0096] A 100 ml Schlenk tube equipped with a magnetic rotor was made to be under a nitrogen
atmosphere, and 5.7 g of tetrakis[tris(dimethylamino)phosphoranylideneamino]phosphonium
chloride (7.4 mmol, manufactured by Sigma-Aldrich) and 16 ml of 2-propanol were added
and dissolved by stirring at 25°C. While maintaining stirring, a solution in which
0.53 g of 85 wt% potassium hydroxide (8.1 mmol, 1.1 mol equivalent to tetrakis[tris(dimethylamino)phosphoranylideneamino]phosphonium
chloride) was dissolved in 2-propanol, was added. After stirring at 25°C for 5 hours,
the precipitated by-product salt was removed by filtration to obtain 33 g of a 2-propanol
solution of monovalent phosphazenium salt-A' at a concentration of 17 mass% in a yield
of 98%. The phosphazenium salt-A' is a phosphazenium salt corresponding to the above
formula (6) in which R
1 is a methyl group, R
2 is a methyl group and X
- is a hydroxy anion. The pH of the obtained phosphazenium salt-A' was 12 (basic).
[0097] Then,
1H-NMR of the obtained phosphazenium salt-A' was measured. The chemical shift of the
monovalent phosphazenium cation in
1H-NMR was 2.62 ppm.
[0098] Further, the phosphazenium salt-A' was subjected to a heat treatment at 120°C for
8 hours, and as a result, a strong odor was generated, and formation of an impurity
peak was confirmed by
1H-NMR.
<Test Example 1>
[0099] To a 100 ml beaker containing a stirrer bar, 10 mg of the 2-propanol solution of
monovalent phosphazenium salt-A obtained in Synthesis Example 1 and 60 ml of a mixed
solution of isopropanol/water=10/6 were added and thoroughly stirred. By dropwise
adding an isopropanol solution of dodecylbenzenesulfonic acid (0.02 mol/L) thereto,
neutralization titration was carried out. The results are shown in Fig. 2.
[0100] Fig. 2 is a diagram showing a change in pH in the neutralization titration of the
phosphazenium salt-A obtained in Synthesis Example 1. In Fig. 2, the vertical axis
represents the pH or the amount of change in pH, and the horizontal axis represents
the ratio (mol/mol) of the number of moles of dodecylbenzenesulfonic acid to the number
of moles of phosphazenium salt-A.
[0101] According to Fig. 2, an equivalence point was observed at the time when about 2 mol
of dodecylbenzenesulfonic acid was dropwise added to 1 mol of monovalent phosphazenium
salt-A, and formation of a divalent phosphazenium salt was confirmed. The divalent
phosphazenium salt is a phosphazenium salt corresponding to the above formula (2)
in which R
1 is a methyl group, R
2 is a methyl group and A
- is a deprotonated form of dodecylbenzenesulfonic acid.
<Test Example 2>
[0102] To a 100 ml beaker containing a stirrer bar, 95 mg of the 2-propanol solution of
monovalent phosphazenium salt-A' obtained in Synthesis Example 2 and 60 ml of methanol
were added and thoroughly stirred. By dropwise adding an isopropanol solution of dodecylbenzenesulfonic
acid (0.02 mol/L) thereto, neutralization titration was carried out.
[0103] An equivalence point was observed at the time when about 2 mol of dodecylbenzenesulfonic
acid was dropwise added to 1 mol of monovalent phosphazenium salt-A', and formation
of a divalent phosphazenium salt was confirmed. The divalent phosphazenium salt is
a phosphazenium salt corresponding to the above formula (3) in which R
1 is a methyl group, R
2 is a methyl group and [A
n-]
m is a deprotonated form of dodecylbenzenesulfonic acid.
<Example 1>
[0104] A 0.2 L four-necked flask containing a stirrer bar was made to be under a nitrogen
atmosphere, and 50 g (36 mmol) of a 2-propanol solution of monovalent phosphazenium
salt-A obtained in Synthesis Example 1 was added. While maintaining stirring, 22 g
of dodecylbenzenesulfonic acid (72 mmol, 2 mol per 1 mol of monovalent phosphazenium
salt) was added thereto. By continuing stirring for 10 minutes, the target divalent
phosphazenium salt-B was obtained. The divalent phosphazenium salt-B is a phosphazenium
salt corresponding to the above formula (2) in which R
1 is a methyl group, R
2 is a methyl group and A
- is a deprotonated form of dodecylbenzenesulfonic acid. The pH of the obtained phosphazenium
salt was 7 (neutral).
[0105] Then,
1H-NMR of the obtained phosphazenium salt-B was measured.
[0106] Fig. 3 is a diagram showing
1H-NMR of the phosphazenium salt-B obtained in Example 1.
1.20 (d, 96H, methyl group of 2-propanol), 0.70 to 1.80 (m, 50H, alkyl group of dodecylbenzenesulfonic
acid), 2.91 (s, 49H, methyl group and additional proton of divalent phosphazenium
salt), 4.02 (sep, 16H, methine of 2-propanol), 7.07 (d, 4H, phenyl group of dodecylbenzenesulfonic
acid), 7.79 (d, 4H, phenyl group of dodecylbenzenesulfonic acid). The chemical shift
of the divalent phosphazenium cation in
1H-NMR was 2.91 ppm, which was shifted to a lower magnetic field as compared with the
monovalent phosphazenium salt-B obtained in Synthesis Example 1. The present inventors
presume that by the change of the valence of the phosphazenium salt from monovalent
to divalent, the cationicity of the phosphazenium salt was increased (the electron
density was decreased).
[0107] Further, the phosphazenium salt-B was subjected to heat treatment at 120°C for 8
hours, and as a result, no odor was confirmed, and no major change in
1H-NMR was confirmed, and it was stable.
[0108] 17 mg of the obtained divalent phosphazenium salt-B was added to 10 g of polyalkylene
oxide having a pH of 6.4 (neutral) and an acetaldehyde volatilization amount of 0.92
ppm, and thoroughly stirred. The obtained polyalkylene oxide remained neutral (pH:
7.3), and the acetaldehyde volatilization amount was reduced to 0.14 ppm. The present
inventors presume that acetaldehyde was captured by the divalent phosphazenium salt
and was less likely to volatilize.
<Example 2>
[0109] A 0.2 L four-necked flask containing a stirrer bar was made to be under a nitrogen
atmosphere, and 50 g (11 mmol) of a 2-propanol solution of monovalent phosphazenium
salt-A' obtained in Synthesis Example 2 was added. While maintaining stirring, 7.5
g of dodecylbenzenesulfonic acid (23 mmol, 2.1 mol to 1 mol of monovalent phosphazenium
salt) was added thereto. After continuing stirring for 10 minutes, the solvent was
removed under reduced pressure to obtain the target divalent phosphazenium salt-B'.
The divalent phosphazenium salt-B' is a phosphazenium salt corresponding to the above
formula (3) in which R
1 is a methyl group, R
2 is a methyl group, and [A
n-]
m is a deprotonated form of dodecylbenzenesulfonic acid. The pH of the obtained phosphazenium
salt was 7 (neutral).
[0110] Then,
1H-NMR of the obtained phosphazenium salt-B' was measured. The chemical shift of the
divalent phosphazenium cation in
1H-NMR was 2.70 ppm, which was shifted to a lower magnetic field as compared with the
monovalent phosphazenium salt-A' obtained in Synthesis Example 2. The present inventors
presume that by the change of the valence of the phosphazenium salt from monovalent
to divalent, the cationicity of the phosphazenium salt was increased (electron density
was decreased).
[0111] Further, the phosphazenium salt-B' was subjected to heat treatment at 120°C for 8
hours, and as a result, no odor was confirmed, and no major change in
1H-NMR was confirmed, and it was stable.
[0112] 31 mg of the obtained divalent phosphazenium salt-B' was added to 10 g of polyalkylene
oxide having a pH of 6.4 (neutral) and an acetaldehyde volatilization amount of 0.92
ppm, and thoroughly stirred. While the obtained polyalkylene oxide was kept neutral
(pH: 7.4), the acetaldehyde volatilization amount was reduced to 0.53 ppm. The present
inventors presume that acetaldehyde was captured by the divalent phosphazenium salt
and was less likely to volatilize.
<Comparative Example 1>
[0113] A 0.2 L four-necked flask containing a stirrer bar was made to be under a nitrogen
atmosphere, and 50 g (36 mmol) of a 2-propanol solution of monovalent phosphazenium
salt-A obtained in Synthesis Example 1 was added. While maintaining stirring, 11 g
of dodecylbenzenesulfonic acid (36 mmol, 1 mol to 1 mol of monovalent phosphazenium
salt) was added thereto. By continuing stirring for 10 minutes, the target monovalent
phosphazenium salt-C was obtained. The monovalent phosphazenium salt-C is a phosphazenium
salt corresponding to the above formula (5) in which R
1 is a methyl group, R
2 is a methyl group and X
- is a deprotonated form of dodecylbenzenesulfonic acid. The pH of the obtained phosphazenium
salt-C was 12, which was strongly basic.
[0114] Then,
1H-NMR of the obtained phosphazenium salt-C was measured.
[0115] Fig. 4 is a diagram showing
1H-NMR of the phosphazenium salt-C obtained in Comparative Example 1.
1.20 (d, 90H, methyl group of 2-propanol), 0.70 to 1.70 (m, 25H, alkyl group of dodecylbenzenesulfonic
acid), 2.83 (s, 48H, methyl group of monovalent phosphazenium salt)), 4.02 (sep, 15H,
methine of 2-propanol), 7.05 (d, 2H, phenyl group of dodecylbenzenesulfonic acid),
7.89 (d, 2H, phenyl group of dodecylbenzenesulfonic acid).
[0116] The chemical shift of the monovalent phosphazenium cation in
1H-NMR was 2.83 ppm, which was a high magnetic field as compared with the divalent
phosphazenium salt-B obtained in Example 1 (Fig. 4). The present inventors presume
that the cationicity was decreased (electron density was increased) as compared with
the divalent phosphazenium salt-B.
[0117] 42 mg of the obtained 2-propanol solution of monovalent phosphazenium salt-C was
added to 10 g of polyalkylene oxide having a pH of 6.4 (neutral) and an acetaldehyde
volatilization amount of 0.92 ppm, and thoroughly stirred. The obtained polyalkylene
oxide had a pH of 10.6 and thus showed a strong basicity. The amount of acetaldehyde
volatilized from the obtained polyalkylene oxide was 0.94 ppm, and no aldehyde scavenging
effect was observed.
<Comparative Example 2>
[0118] A 0.2 L four-necked flask containing a stirrer bar was made to be under a nitrogen
atmosphere, and 50 g (11 mmol) of a 2-propanol solution of monovalent phosphazenium
salt-A' obtained in Synthesis Example 2 was added. While maintaining stirring, 3.6
g of dodecylbenzenesulfonic acid (11 mmol, 1 mol to 1 mol of monovalent phosphazenium
salt) was added thereto. After continuing stirring for 10 minutes, the solvent was
removed under reduced pressure to obtain the desired monovalent phosphazenium salt-C'.
The monovalent phosphazenium salt-C' is a phosphazenium salt corresponding to the
above formula (6) in which R
1 is a methyl group, R
2 is a methyl group and X
- is a deprotonated form of dodecylbenzenesulfonic acid. The obtained phosphazenium
salt-C' had a pH of 12 and thus showed a strong basicity.
[0119] Then,
1H-NMR of the obtained phosphazenium salt-C' was measured. The chemical shift of the
monovalent phosphazenium cation in
1H-NMR was 2.62 ppm, which was a high magnetic field as compared with the divalent
phosphazenium salt-B' obtained in Example 2. The present inventors presume that the
cationicity was decreased (the electron density was increased) as compared with the
divalent phosphazenium salt-B'.
[0120] 22 mg of the obtained monovalent phosphazenium salt-C' was added to 10 g of polyalkylene
oxide having a pH of 6.4 (neutral) and an acetaldehyde volatilization amount of 0.92
ppm, and thoroughly stirred. The obtained polyalkylene oxide had a pH of 8.6 and thus
was basic. The amount of acetaldehyde volatilized from the obtained polyalkylene oxide
was 0.96 ppm, and no aldehyde scavenging effect was observed.
<Example 3>
[0121] A 0.2 L four-necked flask containing a stirrer bar was made to be under a nitrogen
atmosphere, and 50 g (36 mmol) of a 2-propanol solution of monovalent phosphazenium
salt-A obtained in Synthesis Example 1 was added. While maintaining stirring, 23 g
of dodecylbenzenesulfonic acid (76 mmol, 2.1 mol to 1 mol of monovalent phosphazenium
salt) was added thereto. By continuing stirring for 10 minutes, a divalent phosphazenium
salt (a phosphazenium salt corresponding to the above formula (2) in which R
1 is a methyl group, R
2 is a methyl group and A
- is a deprotonated form of dodecylbenzenesulfonic acid) was obtained.
[0122] To a 2 L four-necked flask equipped with a stirring blade, 1,200 g of a polypropylene
oxide having a molecular weight of 7,000 and 2.8 g of the obtained divalent phosphazenium
salt were added and stirred at an internal temperature of 80°C for 1 hour to obtain
1,203 g of a polyalkylene oxide composition containing 2,300 ppm of the divalent phosphazenium
salt. The obtained polyalkylene oxide composition was odorless, had no turbidity,
had a pH of 7.2, a hydroxy value of 24 mgKOH/g, an acetaldehyde volatilization amount
of 0.40 ppm, and a propionaldehyde volatilization amount of 0.04 ppm.
[0123] The obtained polyalkylene oxide composition and MDI were mixed so that the molar
ratio of the isocyanate group (NCO) in MDI to the hydroxy group (OH) in the polyalkylene
oxide composition became 1.5, and reacted until the NCO group was completely consumed,
to synthesize a polyurethane-forming composition. The obtained polyurethane-forming
composition was odorless.
<Example 4>
[0124] In a 2 L autoclave equipped with a stirring blade, 100 g of polypropylene triol having
a molecular weight of 600 and 5.1 g of a 25 mass% 2-propanol solution of 1.3 g (2.5
mmol) of monovalent phosphazenium salt-A obtained in Synthesis Example 1, were added,
and, under an internal temperature of 80°C and a reduced pressure of 0.5 kPa, 2-propanol
was removed. Subsequently, while maintaining an internal temperature of 90°C and a
pressure of at most 0.3 MPa, 946 g of propylene oxide was intermittently supplied
to carry out a polymerization reaction of propylene oxide, and then unreacted propylene
oxide was removed under a reduced pressure of 0.5 kPa. Further, while maintaining
an internal temperature of 130°C and a pressure of at most 0.3 MPa, 173 g of ethylene
oxide was intermittently supplied to carry out a polymerization reaction of ethylene
oxide, and then unreacted ethylene oxide was removed under a reduced pressure of 0.5
kPa. Thereafter, at an internal temperature of 80°C, 2.0 g of dodecylbenzenesulfonic
acid (6.25 mmol, 2.5 mol to 1 mol of monovalent phosphazenium salt) and Irganox 1135
(0.91 g) were added and stirred for 1 hour to obtain 1,210 g of a polyalkylene oxide
composition containing a divalent phosphazenium salt (a phosphazenium salt corresponding
to the above formula (2) in which R
1 is a methyl group, R
2 is a methyl group and A
- is a deprotonated form of dodecylbenzenesulfonic acid). The obtained polyalkylene
oxide composition was odorless, had no turbidity, had a pH of 6.5, had a hydroxy value
of 24 mgKOH/g, had an acetaldehyde volatilization amount of 0.14 ppm, and had a propionaldehyde
volatilization amount of 0.12 ppm.
[0125] The obtained polyalkylene oxide composition and MDI were mixed so that the molar
ratio of the isocyanate group (NCO) in MDI to the hydroxy group (OH) in the polyalkylene
oxide composition became to be 1.5, and reacted until the NCO group was completely
consumed, to synthesize a polyurethane-forming composition. The obtained polyurethane-forming
composition was odorless.
<Example 5>
[0126] In a 2 L autoclave equipped with a stirring blade, 100 g of polypropylene triol having
a molecular weight of 600 and 5.1 g of a 25 mass% 2-propanol solution of 1.3 g (2.5
mmol) of monovalent phosphazenium salt-A obtained in Synthesis Example 1, was added,
and, under an internal temperature of 80°C and a reduced pressure of 0.5 kPa, 2-propanol
was removed. Subsequently, while maintaining an internal temperature of 90°C and a
pressure of at most 0.3 MPa, 946 g of propylene oxide was intermittently supplied
to carry out a polymerization reaction of propylene oxide, and then, under a reduced
pressure of 0.5 kPa, unreacted propylene oxide was removed. Further, while maintaining
an internal temperature of 130°C and a pressure of at most 0.3 MPa, 173 g of ethylene
oxide was intermittently supplied to carry out a polymerization reaction of ethylene
oxide, and then, under a reduced pressure of 0.5 kPa, unreacted ethylene oxide was
removed. Then, at an internal temperature of 80°C, 2.4 g of dodecylbenzenesulfonic
acid (7.5 mmol, 3 mol to 1 mol of monovalent phosphazenium salt) and Irganox 1135
(0.91 g) were added and stirred for 1 hour to obtain 1,210 g of a polyalkylene oxide
composition containing a divalent phosphazenium salt (a phosphazenium salt corresponding
to the above formula (2) in which R
1 is a methyl group, R
2 is a methyl group and A
- is a deprotonated form of dodecylbenzenesulfonic acid). The obtained polyalkylene
oxide composition was odorless, had no turbidity, had a pH of 5.6, had a hydroxy value
of 24 mgKOH/g, had an acetaldehyde volatilization amount of 0.24 ppm, and had a propionaldehyde
volatilization amount of 0.24 ppm.
[0127] The obtained polyalkylene oxide composition and MDI were mixed so that the molar
ratio of the isocyanate group (NCO) in MDI to the hydroxy group (OH) in the polyalkylene
oxide composition became to be 1.5, and reacted until the NCO group was completely
consumed, to synthesize a polyurethane-forming composition. The obtained polyurethane-forming
composition was odorless.
<Example 6>
[0128] In a 2 L autoclave equipped with a stirring blade, 100 g of polypropylene triol having
a molecular weight of 600 and 5.1 g of a 25 mass% 2-propanol solution of 1.3 g (2.5
mmol) of monovalent phosphazenium salt-A obtained in Synthesis Example 1, were added,
and at an internal temperature of 80°C and under a reduced pressure of 0.5 kPa, 2-propanol
was removed. Subsequently, while maintaining an internal temperature of 90°C and a
pressure of at most 0.3 MPa, 946 g of propylene oxide was intermittently supplied
to carry out a polymerization reaction of propylene oxide, and then under a reduced
pressure of 0.5 kPa, unreacted propylene oxide was removed. Further, while maintaining
an internal temperature of 130°C and a pressure of at most 0.3 MPa, 173 g of ethylene
oxide was intermittently supplied to carry out a polymerization reaction of ethylene
oxide, and then under a reduced pressure of 0.5 kPa, unreacted ethylene oxide was
removed. Then, at an internal temperature of 80°C, 0.86 g of p-toluenesulfonic acid
(5.0 mmol, 2 mol to 1 mol of monovalent phosphazenium salt) and Irganox 1135 (0.91
g) were added and stirred for 1 hour to obtain 1,200 g of a polyalkylene oxide composition
containing a divalent phosphazenium salt (a phosphazenium salt corresponding to the
above formula (2) wherein R
1 is a methyl group, R
2 is a methyl group and A
- is a deprotonated form of p-toluenesulfonic acid). The obtained polyalkylene oxide
composition was odorless, had no turbidity, had a pH of 7.3, had a hydroxy value of
24 mgKOH/g and had an aldehyde volatilization amount of 0.3 ppm.
[0129] The obtained polyalkylene oxide composition and MDI were mixed so that the molar
ratio of the isocyanate group (NCO) in MDI to the hydroxy group (OH) in the polyalkylene
oxide composition became to be 1.5, and reacted until the NCO group was completely
consumed, to synthesize a polyurethane-forming composition. The obtained polyurethane-forming
composition was odorless.
<Example 7>
[0130] In a 0.2 L four-necked flask containing a stirrer bar was made to be under a nitrogen
atmosphere, and 50 g (11 mmol) of a 17 mass% 2-propanol solution of monovalent phosphazenium
salt-A' obtained in Synthesis Example 2, was added. While maintaining stirring, 7.5
g of dodecylbenzenesulfonic acid (23 mmol, 2.1 mol to 1 mol of monovalent phosphazenium
salt) was added thereto. After continuing stirring for 10 minutes, the solvent was
removed under reduced pressure to obtain a divalent phosphazenium salt (a phosphazenium
salt corresponding to the above formula (3) in which R
1 is a methyl group, R
2 is a methyl group and [A
n-]
m is a deprotonated form of dodecylbenzenesulfonic acid).
[0131] In a 2 L four-necked flask equipped with a stirring blade, 1,200 g of polypropylene
oxide with acetaldehyde volatilization amount: 0.92 ppm, propionaldehyde volatilization
amount: 3.1 ppm, pH: 6.4 (neutral), and hydroxy value of 24 mg KOH/g and 3.7 g of
the obtained divalent phosphazenium salt were added, and stirred at an internal temperature
of 80°C for 1 hour to obtain 1,204 g of a polyalkylene oxide composition containing
3,100 ppm of a divalent phosphazenium salt (a phosphazenium salt corresponding to
the above formula (3) in which R
1 is a methyl group, R
2 is a methyl group and [A
n-]
m is a deprotonated form of dodecylbenzenesulfonic acid). The obtained polyalkylene
oxide composition was odorless, had no turbidity, had a pH of 7.4 (neutral), and had
a hydroxy value of 24 mgKOH/g. The acetaldehyde volatilization amount was reduced
to 0.53 ppm and the propionaldehyde volatilization amount was reduced to 0.11 ppm.
[0132] The obtained polyalkylene oxide composition and MDI were mixed so that the molar
ratio of the isocyanate group (NCO) in MDI to the hydroxy group (OH) in the polyalkylene
oxide composition became to be 1.5, and reacted until the NCO group was completely
consumed, to synthesize a polyurethane-forming composition. The obtained polyurethane-forming
composition was odorless.
<Comparative Example 3>
[0133] In a 2 L autoclave equipped with a stirring blade, 100 g of polypropylene triol having
a molecular weight of 600 and 5.1 g of a 25 mass% 2-propanol solution of 1.3 g (2.5
mmol) of monovalent phosphazenium salt-A obtained in Synthesis Example 1, were added,
and under an internal temperature of 80°C and a reduced pressure of 0.5 kPa, 2-propanol
was removed. Subsequently, while maintaining an internal temperature of 90°C and a
pressure of at most 0.3 MPa, 946 g of propylene oxide was intermittently supplied
to carry out a polymerization reaction of propylene oxide, and then under a reduced
pressure of 0.5 kPa, unreacted propylene oxide was removed. Further, while maintaining
an internal temperature of 130°C and a pressure of at most 0.3 MPa, 173 g of ethylene
oxide was intermittently supplied to carry out a polymerization reaction of ethylene
oxide, and then under a reduced pressure of 0.5 kPa, unreacted ethylene oxide was
removed. Then, at an internal temperature of 85°C, 30 g of water and 12 g of KYOWARD
700SEN-S (adsorbent manufactured by Kyowa Chemical Industry Co., Ltd.) were added
and stirred for 1 hour. Further, the temperature was raised to 120°C, the mixture
was stirred for 3 hours, dehydration treatment was carried out for 3 hours under a
reduced pressure of 0.5 kPa, and then the adsorbent was removed by filtration to obtain
1,210 g of a polyalkylene oxide composition containing no divalent phosphazenium salt.
The obtained polyalkylene oxide composition was odorless, had no turbidity, had a
pH of 6.8, had a hydroxy value of 24 mgKOH/g, had a high acetaldehyde volatilization
amount of 0.92 ppm, and had a high propionaldehyde volatilization amount of 3.1 ppm.
[0134] The obtained polyalkylene oxide composition and MDI were mixed so that the molar
ratio of the isocyanate group (NCO) in MDI to the hydroxy group (OH) in the polyalkylene
oxide composition became to be 1.5, and reacted until the NCO group was completely
consumed, to synthesize a polyurethane-forming composition. The obtained polyurethane-forming
composition had a slight odor.
<Comparative Example 4>
[0135] In a 2 L autoclave equipped with a stirring blade, 100 g of polypropylene triol having
a molecular weight of 600 and 5.1 g of a 25 mass% 2-propanol solution of 1.3 g (2.5
mmol) of monovalent phosphazenium salt-A obtained in Synthesis Example 1 were added,
and under an internal temperature of 80°C and a reduced pressure of 0.5 kPa, 2-propanol
was removed. Subsequently, while maintaining an internal temperature of 90°C and a
pressure of at most 0.3 MPa, 946 g of propylene oxide was intermittently supplied
to carry out a polymerization reaction of propylene oxide, and then under a reduced
pressure of 0.5 kPa, unreacted propylene oxide was removed. Further, while maintaining
an internal temperature of 130°C and a pressure of at most 0.3 MPa, 173 g of ethylene
oxide was intermittently supplied to carry out a polymerization reaction of ethylene
oxide, and then under a reduced pressure of 0.5 kPa, unreacted ethylene oxide was
removed. Then, at an internal temperature of 80°C, 0.8 g of dodecylbenzenesulfonic
acid (2.5 mmol, 1.0 mol to 1 mol of monovalent phosphazenium salt) and Irganox 1135
(0.91 g) were added, and stirred for 1 hour to obtain 1,210 g of a polyalkylene oxide
composition containing a monovalent phosphazenium salt (a phosphazenium salt corresponding
to the above formula (5) in which R
1 is a methyl group, R
2 is a methyl group and X
- is a deprotonated form of dodecylbenzenesulfonic acid). The obtained polyalkylene
oxide composition had an odor, was not cloudy, had a pH of 8.4, and showed basicity.
[0136] The obtained polyalkylene oxide composition and MDI were mixed so that the molar
ratio of the isocyanate group (NCO) in MDI to the hydroxy group (OH) in the polyalkylene
oxide composition became to be 1.5, but because the composition was basic, it was
not possible to obtain a polyurethane forming composition.
<Comparative Example 5>
[0137] In a 2 L autoclave equipped with a stirring blade, 100 g of polypropylene triol having
a molecular weight of 600 and 5.1 g of a 25 mass% 2-propanol solution of 1.3 g (2.5
mmol) of monovalent phosphazenium salt-A obtained in Synthesis Example 1 were added,
and under an internal temperature of 80°C and a reduced pressure of 0.5 kPa, 2-propanol
was removed. Subsequently, while maintaining an internal temperature of 90°C and a
pressure of at most 0.3 MPa, 946 g of propylene oxide was intermittently supplied
to carry out a polymerization reaction of propylene oxide, and then under a reduced
pressure of 0.5 kPa, unreacted propylene oxide was removed. Further, while maintaining
an internal temperature of 130°C and a pressure of at most 0.3 MPa, 173 g of ethylene
oxide was intermittently supplied to carry out a polymerization reaction of ethylene
oxide, and then under a reduced pressure of 0.5 kPa, unreacted ethylene oxide was
removed. Then, at an internal temperature of 80°C, 5.0 mL of a 1.0 mol/L hydrochloric
acid aqueous solution (5.0 mmol, 2 mol to 1 mol of monovalent phosphazenium salt)
and Irganox 1135 (0.91 g) were added, and under reduced pressure, water was removed,
to obtain 1,210 g of a polyalkylene oxide composition containing a divalent phosphazenium
salt (a phosphazenium salt corresponding to the above formula (2) in which R
1 is a methyl group, R
2 is a methyl group and A
- is a chlorine anion). The obtained polyalkylene oxide composition was odorless, was
cloudy and had a pH of 7.2.
[0138] The obtained polyalkylene oxide composition and MDI were mixed so that the molar
ratio of the isocyanate group (NCO) in MDI to the hydroxy group (OH) in the polyalkylene
oxide composition became to be 1.5, to synthesize a polyurethane-forming composition.
The obtained polyurethane-forming composition was cloudy due to the cloudiness of
the polyalkylene oxide composition.
<Comparative example 6>
[0139] In a 2 L autoclave equipped with a stirring blade, 100 g of polypropylene triol having
a molecular weight of 600 and 11 g (2.5 mmol) of a 17 mass% 2-propanol solution of
monovalent phosphazenium salt-A' obtained in Synthesis Example 2 were added, and under
an internal temperature of 80°C and a reduced pressure of 0.5 kPa, 2-propanol was
removed. Subsequently, while maintaining an internal temperature of 90°C and a pressure
of at most 0.3 MPa, 946 g of propylene oxide was intermittently supplied to carry
out a polymerization reaction of propylene oxide, and then under a reduced pressure
of 0.5 kPa, unreacted propylene oxide was removed. Further, while maintaining an internal
temperature of 130°C and a pressure of at most 0.3 MPa, 173 g of ethylene oxide was
intermittently supplied to carry out a polymerization reaction of ethylene oxide,
and then under a reduced pressure of 0.5 kPa, unreacted ethylene oxide was removed.
Then, at an internal temperature of 85°C, 30 g of water and 12 g of KYOWARD 700SEN-S
(adsorbent manufactured by Kyowa Chemical Industry Co., Ltd.) were added and stirred
for 1 hour. Further, the temperature was raised to 120°C, the mixture was stirred
for 3 hours, dehydration treatment was carried out for 3 hours under a reduced pressure
of 0.5 kPa, and then the adsorbent was removed by filtration to obtain 1,210 g a polyalkylene
oxide composition containing no divalent phosphazenium salt. The obtained polyalkylene
oxide composition was odorless, had no turbidity, had a pH of 6.9 (neutral), and had
a hydroxy value of 24 mgKOH/g. Further, the obtained polyalkylene oxide composition
had a high acetaldehyde volatilization amount of 0.95 ppm and a high propionaldehyde
volatilization amount of 3.3 ppm.
[0140] The obtained polyalkylene oxide composition and MDI were mixed so that the molar
ratio of the isocyanate group (NCO) in MDI to the hydroxy group (OH) in the polyalkylene
oxide composition became to be 1.5, and reacted until the NCO group was completely
consumed, to synthesize a polyurethane-forming composition. The obtained polyurethane-forming
composition had a slight odor.
<Comparative Example 7>
[0141] A 0.2 L four-necked flask containing a stirrer bar was made to be under a nitrogen
atmosphere, and 50 g (11 mmol) of a 17 mass% 2-propanol solution of monovalent phosphazenium
salt-A' obtained in Synthesis Example 2, was added. While maintaining stirring, 3.6
g of dodecylbenzenesulfonic acid (11 mmol, 1.0 mol to 1 mol of monovalent phosphazenium
salt) was added thereto. After continuing stirring for 10 minutes, the solvent was
removed under reduced pressure to obtain a monovalent phosphazenium salt (cationic
species was a tetrakis[tris(dimethylamino)phosphoranylideneamino]phosphonium cation,
and anionic species was a protonated form of dedecylbenzenesulfonic acid).
[0142] In a 2 L four-necked flask equipped with a stirring blade, 1,200 g of polypropylene
oxide with acetaldehyde volatilization amount: 0.92 ppm, propionaldehyde volatilization
amount: 3.1 ppm, pH: 6.4 (neutral) and hydroxy value of 24 mg KOH/g, and 2.8 g of
the obtained monovalent phosphazenium salt, were added and stirred at an internal
temperature of 80°C for 1 hour, to obtain 1,203 g of a polyalkylene oxide composition
containing 2,300 ppm of a monovalent phosphazenium salt (cation species was tetrakis[tris(dimethylamino)phosphoranylideneamino]phosphonium
cation and anion species was a deprotonated form of dodecylbenzenesulfonic acid).
The obtained polyalkylene oxide composition had an odor, was not cloudy, had a pH
of 8.6 and showed basicity.
[0143] The obtained polyalkylene oxide composition and MDI were mixed so that the molar
ratio of the isocyanate group (NCO) in MDI to the hydroxy group (OH) in the polyalkylene
oxide composition became to be 1.5, but because the composition was basic, it was
not possible to obtain a polyurethane forming composition.
<Comparative Example 8>
[0144] A 0.2 L four-necked flask containing a stirrer bar was made to be under a nitrogen
atmosphere, and 50 g (11 mmol) of a 17 mass% 2-propanol solution of monovalent phosphazenium
salt-A' obtained in Synthesis Example 2, was added. While maintaining stirring, 23
mL of a 1.0 mol/L hydrochloric acid solution (23 mmol, 2.1 mol to 1 mol of monovalent
phosphazenium salt) was added thereto. After continuing stirring for 10 minutes, the
solvent was removed under reduced pressure to obtain a divalent phosphazenium salt
(a phosphazenium salt corresponding to the above formula (3) in which R
1 is a methyl group, R
2 is a methyl group and [A
n-]
m is a chlorine anion).
[0145] In a 2 L four-necked flask equipped with a stirring blade, 1,200 g of polypropylene
oxide having a pH of 6.4 (neutral) and a hydroxy value of 24 mgKOH/g, and 2.1 g of
the obtained divalent phosphazenium salt, were added and stirred at a temperature
of 80°C for 1 hour, to obtain 1,202 g of a polyalkylene oxide composition containing
2,300 ppm of a divalent phosphazenium salt (a phosphazenium salt corresponding to
the above formula (3) in which R
1 is a methyl group, R
2 is a methyl group and [A
n-]
m is a chlorine anion). The obtained polyalkylene oxide composition was odorless, was
cloudy and had a pH of 7.1.
[0146] The obtained polyalkylene oxide composition and MDI were mixed so that the molar
ratio of the isocyanate group (NCO) in MDI to the hydroxy group (OH) in the polyalkylene
oxide composition became to be 1.5, to synthesize a polyurethane-forming composition.
The obtained polyurethane-forming composition was cloudy due to the cloudiness of
the polyalkylene oxide composition.
[0147] The divalent phosphazenium salt according to one embodiment of the present invention
is neutral and is excellent in thermal stability and aldehyde scavenging effect. Therefore,
for example, by adding the divalent phosphazenium salt to a polyalkylene oxide, it
is possible to obtain a polyalkylene oxide having a small amount of aldehyde volatilization.
Such a polyalkylene oxide can be expected to be applied to polyurethanes, polyesters,
surfactants, lubricants, etc.
[0148] Further, the polyalkylene oxide composition according to one embodiment of the present
invention is odorless, has no turbidity and has a small amount of aldehyde volatilization,
and thus is useful as a polyurethane raw material, a polyester raw material, a surfactant
raw material, a lubricant raw material, etc. In particular, by reacting with various
isocyanate compounds, it is expected to be developed into rigid foams to be used for
heat insulation materials, into soft foams to be used for automobile seats, cushions,
bedding, etc. and into adhesives, paints, sealing materials, thermosetting elastomers
and thermoplastic elastomers.
[0149] In the foregoing, the present invention has been described in detail and with reference
to specific embodiments, but it is apparent to those skilled in the art that various
changes and modifications can be made without departing from the spirit and scope
of the invention.